CN106868246A - A kind of environment-friendly type phosphorus pig iron additive, its preparation method and phosphorous pig iron carbon increasing sulfur method - Google Patents
A kind of environment-friendly type phosphorus pig iron additive, its preparation method and phosphorous pig iron carbon increasing sulfur method Download PDFInfo
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- CN106868246A CN106868246A CN201710171028.5A CN201710171028A CN106868246A CN 106868246 A CN106868246 A CN 106868246A CN 201710171028 A CN201710171028 A CN 201710171028A CN 106868246 A CN106868246 A CN 106868246A
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C1/00—Refining of pig-iron; Cast iron
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C1/00—Refining of pig-iron; Cast iron
- C21C1/02—Dephosphorising or desulfurising
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C1/00—Refining of pig-iron; Cast iron
- C21C1/02—Dephosphorising or desulfurising
- C21C1/025—Agents used for dephosphorising or desulfurising
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
- C25C3/08—Cell construction, e.g. bottoms, walls, cathodes
- C25C3/12—Anodes
Abstract
A kind of environment-friendly type phosphorus pig iron additive, its preparation method and phosphorous pig iron carbon increasing sulfur method, it is related to aluminum electrolysis field, the environment-friendly type phosphorus pig iron additive is pressed into pelletizing and is obtained by 95.5%~98.5% carbon material of percentage, 1.0%~3.5% binding agent and 0.5%~1.0% carbonate, carbon material is the solid carbon obtained through vacuum metallurgy treatment waste cathode carbon block, the preparation method is simple, obtained additive low cost, the carburetting desulfurized effect to the phosphorus pig iron is good；The phosphorous pig iron carbon increasing sulfur method is to be layered to add additive and phosphorus pig iron raw material in intermediate frequency furnace, melting is carried out again, the carbon absorption rate of the method is high, desulfurized effect is good, it is effectively reduced material dust collector in phosphorous pig iron carbon increasing sweetening process simultaneously, improve workshop condition, and phosphorus molten pig iron good fluidity, the phosphorus pig iron for obtaining meets the demand of the phosphorus pig iron used for casting pre-roasting anode.
Description
Technical field
The present invention relates to a kind of aluminum electrolysis field, and more particularly to a kind of environment-friendly type phosphorus pig iron additive, its preparation
Method and phosphorous pig iron carbon increasing sulfur method.
Background technology
In aluminum electrolysis, prebaked anode is referred to as " heart " of electrolytic cell, and prebaked anode is led by anode block, aluminium
Bar is constituted, specifically aluminum guide steel pawl and anode block carbon bowl gap cast phosphorus molten pig iron, after cooling anode block and
Aluminum guide is combined as a whole, and the phosphorus pig iron plays connection and conductive effect.It is to reduce electrolytic aluminium to reduce prebaked anode Fe-C pressure drops
One of mode of production cost, and practice have shown that, the element proportioning for adjusting the phosphorus pig iron is the best mode for reducing Fe-C pressure drops.
In the phosphorus pig iron, C can change the elementary organization of the phosphorus pig iron, and then change intensity, hardness and the mobility of the phosphorus pig iron,
C content is higher, and phosphorus molten pig iron mobility is better, and the amount of contraction of normal temperature cooling is smaller, more advantageously reduces Fe-C pressure drops.Si is to promote
Enter graphite element, the mobility of iron liquid can be changed, reduce the contraction of the phosphorus pig iron.P plays a part of to increase iron liquid mobility, can
Increase the cold brittleness of the phosphorus pig iron, be conducive to reducing the load of phosphorus pig iron ring press releasing machine, if but P additions are excessive, and it will be with steel pawl
Reaction.Mn is carbide-forming element, increases intensity, the hardness of the phosphorus pig iron, makes dense structure, reduces the mobility of iron liquid, is had
The effect of desulfurization.S is to hinder graphited element, it is possible to decrease the mobility of molten hot metal, increases phosphorus pig iron hot tearing.Although phosphorus is given birth to
C, P, S, Si, Mn in iron are respectively provided with certain effect, but in actual production process, the C for melting down the phosphorus pig iron is burnt, P, S
Enrichment, causes phosphorus pig iron Fe-C pressure drops to be increased, and the mobility and electric conductivity of the phosphorus pig iron weaken, performance reduction.Accordingly, it would be desirable to
It is adjusted by each element (C, the Si, Mn) content melted down in the phosphorus pig iron, mainly C content is adjusted, i.e. counterweight
The phosphorus pig iron of new melting carries out carburetting desulfurization process, to reach the purpose of enhancing phosphorus pig iron mobility and electric conductivity.
The Chinese patent of publication number CN102560225B discloses a kind of method of phosphorous pig iron carbon increasing, and the carburant selects stone
Ink, real density is 2.0~2.2g/cm3, the addition of carburant is the 0.46~1.9% of phosphorus pig iron gross weight, merely using excellent
Matter graphite carries out carburetting, relatively costly, and the Adding Way of the carburant is that at least 2 times additions increase in the phosphorus pig iron of molten condition
Carbon agent, it is the 0.1~1.0% of phosphorus molten pig iron weight that the weight of carburant is added every time, before adding carburant, to molten condition
The phosphorus pig iron carries out dragging for slag.But graphite easily swims in high temperature liquid iron surface during addition, cause oxidation, and easily fly upward,
Cause carburant graphite that larger physics and chemical loss occurs, finally result in that carbon absorption rate is low, carburetting effect is poor.
The Chinese patent of publication number CN105154621A discloses a kind of preparation method of steel-smelting carburant, the method purport
The produced tiny char particle in coke-oven plant's dry coke quenching production process is maximally utilised, by sieving, drying, sieve again
Technique prepares the carburant for STEELMAKING PRODUCTION, but because dry coke quenching is to use inert gas by red Jiao's (1000 DEG C) cooling down
The coke powder to generation of gathering dust in room temperature process, therefore coke powder is second-rate, and degree of graphitization is not high, and the coke powder is used as carburant
Carburetting effect it is poor, no more than the carburetting effect of calcined coke, more cannot be with graphite-phase ratio.
The Chinese patent of publication number CN101570803B discloses a kind of phosphorous pig iron desulfurizer used for casting pre-roasting anode, the skill
The composition that desulfurizing agent is disclosed in art is：2~4% graphite, 35~45% CaO, 3~5% CaF2, 1~3%
Na2CO3, 40~50% Na2SiO3, 1~3% FeO, the addition of desulfurizing agent is 2.5%, and the desulfurizing agent is in 1.6 tons of sensings
Used on stove, the phosphorated pig iron composition and performance of production reach use requirement, but the technology to realize recycling for the phosphorus pig iron,
Desulfurizing agent is not use only, graphite is also added as carburetant, raw material is complicated, processing cost is expensive.
Accordingly, it would be desirable to one kind can good to phosphorous pig iron carbon increasing, desulfurization, and effect, low cost carburetting desulfurizing agent and increasing simultaneously
Carbon sulfur method.
The content of the invention
It is an object of the invention to provide a kind of environment-friendly type phosphorus pig iron additive, low cost, can simultaneously to phosphorous pig iron carbon increasing,
Desulfurization, and carbon absorption rate is high, desulfurized effect is good.
Another object of the present invention is to provide a kind of preparation method of environment-friendly type phosphorus pig iron additive, the method is simple,
Obtained additive low cost, the carburetting desulfurized effect to the phosphorus pig iron is good.
Another object of the present invention is to provide a kind of phosphorous pig iron carbon increasing sulfur method, using above-mentioned carburetting desulfurizing agent to phosphorus
The pig iron carries out carburetting, desulfurization, and carbon absorption rate is high, carburetting desulfurized effect is good, and desulfurized effect is good, while being effectively reduced the phosphorus pig iron
Material dust collector in carburetting sweetening process, improves workshop condition.
The present invention is solved its technical problem and is realized using following technical scheme.
The present invention proposes a kind of environment-friendly type phosphorus pig iron additive, and it is made up of following raw material, percentage, raw material
Including 95.5%~98.5% carbon material, 1.0%~3.5% binding agent and 0.5%~1.0% carbonate, wherein,
Carbon material is the solid carbon obtained through vacuum metallurgy treatment waste cathode carbon block, and binding agent by being 1 in mass ratio:1.5~2 nothing
Machine binding agent and organic binder bond are constituted.
Further, in present pre-ferred embodiments, the particle diameter of waste cathode carbon block is 10~50mm；Solid carbon it is main by
C、CaF2, NaF composition, wherein C content be not less than 98%.
Further, in present pre-ferred embodiments, inorganic binder includes alkali silicate, fluosilicate, silicon
In aluminate, phosphate, metal alkoxide, magnesium fluosilicate, ammonium chloride, ammonium phosphate, zinc oxide, aluminium hydroxide, aluminium borate at least
It is a kind of.
Further, in present pre-ferred embodiments, organic binder bond includes starch, sodium carboxymethylcellulose, poly- second
At least one in enol, sodium bentonite, sodium humate, polytetrafluoroethylene (PTFE), butadiene-styrene rubber.
A kind of preparation method of environment-friendly type phosphorus pig iron additive, it includes procedure below：
Percentage, prepares raw material, and raw material includes 95.5%~98.5% carbon material, 1.0%~3.5%
Binding agent and 0.5%~1.0% carbonate, wherein, carbon material through vacuum metallurgy treatment waste cathode carbon block obtain
Solid carbon, binding agent by being 1 in mass ratio:1.5~2 inorganic binder and organic binder bond composition；
Organic binder bond and 80~100 DEG C of water are pressed 7~10:1 mass ratio mixing, adds inorganic viscous under agitation
Knot agent, and carbonate is added, 0.5~1.0h is stirred, room temperature is naturally cooled to, obtain binding material；By carbon material and bonding
Material mixes 5~10min, obtains additive paste；Additive paste is pressed into pelletizing, ball-making pressure index on marble forming machine
12~18MPa is controlled to, pelletizing, a diameter of 5~15mm of pelletizing is obtained；Pelletizing is placed in 110~180 DEG C of baking oven and is dried
0.5~3.0h.
Further, in present pre-ferred embodiments, solid carbon is obtained in accordance with the following methods：Waste cathode carbon block is placed in
In vacuum metallurgy furnace, distillation is vacuumized and heats, vacuum is 10~50Pa, and heating vapo(u)rizing temperature is 850~1200 DEG C, heating
Distillation time is 1~3h, and distillation is collected in vacuum metallurgy furnace body after finishing and obtains solid carbon.
A kind of phosphorous pig iron carbon increasing sulfur method, it includes procedure below：
By above-mentioned environment-friendly type phosphorus pig iron additive and phosphorus pig iron raw material to be layered addition in the way of be placed in intermediate frequency furnace, and
Carry out melting.
Further, in present pre-ferred embodiments, additive gross weight account for phosphorus pig iron raw material gross weight 0.8~
2.0%.
Further, in present pre-ferred embodiments, phosphorus pig iron raw material includes melting down the phosphorus pig iron and element raw material, adds
The Adding Way of agent and phosphorus pig iron raw material is：One layer of additive first is laid at intermediate frequency furnace bottom, multilayer pantogen is then laid successively
Material and additive, finally lay one layer and melt down the phosphorus pig iron.
Further, in present pre-ferred embodiments, smelting temperature is 1400~1500 DEG C, is constantly stirred in fusion process
Mix；Phosphorus molten pig iron to molten condition carries out 2~3 slag hittings treatment, and temperature is down to 1350~1400 DEG C of cast of coming out of the stove.
The environment-friendly type phosphorus pig iron additive of the embodiment of the present invention, its preparation method and phosphorous pig iron carbon increasing sulfur method it is beneficial
Effect is：The environment-friendly type phosphorus pig iron additive of the embodiment of the present invention be by percentage 95.5%~98.5% charcoal
Cellulosic material, 1.0%~3.5% binding agent and 0.5%~1.0% carbonate be pressed into pelletizing be obtained, carbon material be through
The solid carbon that vacuum metallurgy treatment waste cathode carbon block is obtained, the preparation method is simple, obtained low cost, the carburetting to the phosphorus pig iron
Desulfurized effect is good；The phosphorous pig iron carbon increasing sulfur method of the embodiment of the present invention is added in intermediate frequency furnace by the way of addition is layered
Carburetting desulfurizing agent and phosphorus pig iron raw material, then carry out the purpose that melting reaches carburetting desulfurization, the carbon absorption rate of the method is high, carburetting takes off
Sulphur effect is good, and desulfurized effect is good, while being effectively reduced material dust collector in phosphorous pig iron carbon increasing sweetening process, improves workshop ring
Border, and phosphorus molten pig iron good fluidity, the phosphorus pig iron for obtaining meet the demand of the phosphorus pig iron used for casting pre-roasting anode.
Brief description of the drawings
Technical scheme in order to illustrate more clearly the embodiments of the present invention, below will be attached to what is used needed for embodiment
Figure is briefly described, it will be appreciated that the following drawings illustrate only certain embodiments of the present invention, thus be not construed as it is right
The restriction of scope, for those of ordinary skill in the art, on the premise of not paying creative work, can also be according to this
A little accompanying drawings obtain other related accompanying drawings.
Fig. 1 is the material phase analysis figure of solid carbon obtained through vacuum metallurgy treatment waste cathode carbon block in the embodiment of the present invention 1.
Specific embodiment
To make the purpose, technical scheme and advantage of the embodiment of the present invention clearer, below will be in the embodiment of the present invention
Technical scheme be clearly and completely described.Unreceipted actual conditions person, builds according to normal condition or manufacturer in embodiment
The condition of view is carried out.Agents useful for same or the unreceipted production firm person of instrument, are the conventional product that can be obtained by commercially available purchase
Product.
Environment-friendly type phosphorus pig iron additive following to the embodiment of the present invention, its preparation method and phosphorous pig iron carbon increasing sulfur method
It is specifically described.
Feature of the invention and performance are described in further detail with reference to embodiments.
A kind of environment-friendly type phosphorus pig iron additive of the embodiment of the present invention, it is made up of following raw material, percentage, former
Material includes 95.5%~98.5% carbon material, 1.0%~3.5% binding agent and 0.5%~1.0% melting promotor.
Wherein, carbon material is the solid carbon obtained through vacuum metallurgy treatment waste cathode carbon block, and waste cathode carbon block is mainly
The aluminium electroloysis electrolytic cell waste liner cathode material that stopping production overhaul is obtained after 1000~2000 days run, i.e. waste cathode carbon block,
The particle diameter of waste cathode carbon block is 10~50mm, by the use of waste cathode carbon block as the raw material of carbon material, it is possible to achieve resource comprehensive
Utilize, the purpose for turning waste into wealth.Fixed carbon is main by C, CaF2, NaF compositions, with the double action for increasing charcoal and desulfurization, wherein C
Content is not less than 98%, and the real density of the fixed carbon is 2.02~2.08g/cm3；Granularity is in below 5mm.
Wherein, binding agent plays a part of gelling to solid carbon, and the binding agent is specifically by being in mass ratio 1:1.5~2
Inorganic binder and organic binder bond composition, improve solidification effect.Wherein, inorganic binder includes alkali silicate (silicon
Sour potassium, sodium metasilicate, magnesium silicate, calcium silicates, alumina silicate etc.), fluosilicate (potassium fluosilicate, prodan, calcium fluosilicate, fluorine silicon
Sour magnesium, aluminum fluosilicate etc.), alumino-silicate (potassium aluminosilicate, sodium silicoaluminate, ca aluminosilicate etc.), phosphate, metal alkoxide, fluorine silicon
At least one in sour magnesium, ammonium chloride, ammonium phosphate, zinc oxide, aluminium hydroxide, aluminium borate, preferably alkali silicate, fluorine silicon
At least one in hydrochlorate, alumino-silicate；Organic binder bond includes starch, sodium carboxymethylcellulose, polyvinyl alcohol, Na-bentonite
At least one in soil, sodium humate, polytetrafluoroethylene (PTFE), butadiene-styrene rubber, preferably starch, sodium carboxymethylcellulose, polyethylene
At least one in alcohol.
Wherein, melting promotor is carbonate, specifically includes sodium carbonate, potassium carbonate etc., but not comprising calcium carbonate.
The embodiment of the present invention also provides a kind of preparation method of environment-friendly type phosphorus pig iron additive, and it mainly includes following step
Suddenly：
It is S1, broken：The solid carbon block obtained through vacuum metallurgy treatment waste cathode carbon block is crushed, and is sieved by 5mm
Net, obtains carbon material solid carbon, i.e. carburetting desulfurizing agent, and broken purpose is to obtain the solid carbon of particle uniformity.
Wherein, solid carbon is obtained in accordance with the following methods：Waste cathode carbon block is placed in vacuum metallurgy furnace, is vacuumized and is heated
Distillation, vacuum is 10~50Pa, and heating vapo(u)rizing temperature is 850~1200 DEG C, and heating distillation time is 1~3h, and distillation is finished
Collected in vacuum metallurgy furnace body afterwards and obtain solid carbon.
S2, dispensing：Percentage, prepares raw material, and raw material includes 95.5%~98.5% solid carbon, 1.0%
~3.5% binding agent and 0.5%~1.0% carbonate, wherein, binding agent by being 1 in mass ratio:1.5~2 it is inorganic viscous
Knot agent and organic binder bond composition, inorganic binder preferably include alkali silicate, fluosilicate, alumino-silicate, phosphate,
At least one in metal alkoxide, magnesium fluosilicate, ammonium chloride, ammonium phosphate, zinc oxide, aluminium hydroxide, aluminium borate, organic binder bond
Preferably include starch, sodium carboxymethylcellulose, polyvinyl alcohol, sodium bentonite, sodium humate, polytetrafluoroethylene (PTFE), butadiene-styrene rubber
In at least one.
S3, configuration binding material：First, by organic binder bond and 80~100 DEG C of water according to 7~10:1 mass ratio
Mixing, adds inorganic binder under fast stirring, and adds carbonate, stirs 0.5~1.0h, naturally cools to room temperature, obtains
To binding material, it should be noted that to control the consumption of binding agent, water in the configuration process of binding material, temperature and stir
Mix the time.
S4, prepare additive paste：Binding material will immediately carry out subsequent formulation after configuring, by solid carbon and bonding material
Material is mixed to form mixture, stirs 5~10min, obtains additive paste.
S5, pelletizing processed：Pelletizing processed be it is a kind of by dispersed substance by being pressed into the technology of solid shape, the embodiment of the present invention
In be specifically that additive paste is pressed into pelletizing on marble forming machine, ball-making pressure norm controlling is 12~18MPa, obtains pelletizing,
The size of pelletizing can be selected as needed, and general control is in a diameter of 5~15mm.
S6, drying：The effect of drying is to remove the moisture that includes of pelletizing, additive is more solidified, solid, due in step
Water is added during rapid S2 configurations binding material, therefore needs to carry out drying and processing, be specifically by ball in the embodiment of the present invention
Group is placed in and 0.5~3.0h is dried in 110~180 DEG C of baking oven.
The embodiment of the present invention also provides a kind of phosphorous pig iron carbon increasing sulfur method, and it includes procedure below：
First, by environment-friendly type phosphorus pig iron additive obtained above and phosphorus pig iron raw material to be layered addition in the way of be placed in
In frequency stove.
According to phosphorus pig iron assay result is melted down to original, need to be in phosphorous pig iron carbon increasing sweetening process be melted down, appropriate supplement
A small amount of element raw material (predominantly ferromanganese, the pig iron, ferrosilicon), because the phosphorus pig iron is during being recycled for multiple times, especially
It is the chemical composition of the former phosphorus pig iron disequilibrium through after the washing away of severe corrosive electrolyte in electrolytic cell, is mainly manifested in
The slightly reduction of Mn, Si element, P, S element is stablized relatively.Therefore, according to result of calculation, being carried out suitably to respective element raw material
Supplement.Phosphorus pig iron raw material includes melting down the phosphorus pig iron and element raw material, need to ensure the bottom for additive, and the superiors give birth to melt down phosphorus
Iron, middle each layer alternately can lay other the element raw materials and additive that need to supplement, additive and the phosphorus pig iron according to actual conditions
The Adding Way of raw material is：First intermediate frequency furnace bottom lay one layer of additive, then successively laying multilayer supplement element raw material and
Additive, finally lays one layer and is melting down the phosphorus pig iron, melts down the phosphorus pig iron and element raw material collectively constitutes the phosphorus pig iron, is counted according to theory
Calculate additive gross weight accounts for phosphorus pig iron raw material gross weight 0.8%~2.0%.Further, phosphorus pig iron raw material by weight hundred
Fraction meter specifically includes 90.5%~94.0% and melts down the phosphorus pig iron, 0.55%~0.90% ferromanganese, 5.4%~8.5%
The pig iron, 0.05%~0.10% ferrosilicon.The method that increases of corresponding additive and phosphorus pig iron raw material is：First add at intermediate frequency furnace bottom
Enter one layer of additive, then sequentially add the ferromanganese for melting down the phosphorus pig iron, additive and supplement, melt down the phosphorus pig iron, additive and benefit
The pig iron for filling, melts down the ferrosilicon of the phosphorus pig iron, additive and supplement, is eventually adding and melts down the phosphorus pig iron.
Then, directly carry out the phosphorus pig iron and melt down melting, need to control smelting temperature in fusion process, the present invention is implemented
Example controls smelting temperature for 1400~1500 DEG C, and is stirred continuously in fusion process, additive is melted rapidly；It is right to also need to
The phosphorus molten pig iron of molten condition carries out 2~3 slag hittings treatment, and the purpose of slag hitting is to remove the impurity floated in high temperature liquid iron, main
To treat that temperature is down to 1350~1400 DEG C of cast of coming out of the stove comprising oxide, sulfide, carbide etc..
To sum up analyze, the environment-friendly type phosphorus pig iron additive of the embodiment of the present invention can effectively improve the carbon content in the phosphorus pig iron,
Sulfur content is reduced, the main component of carburetting ball is primarily due to for solid carbon, and adds binding agent, melting promotor, by pelletizing processed,
Apply layering to feed intake, can improve that carbon absorption rate, carburetting effect are good, desulfurized effect is good, carburetting desulfurizing agent can be reduced again and is being used
During the material dust collector problem that causes, environmental protection finally realizes optimal carburetting desulfurized effect；And the technological operation
Simply, with low cost, carburetting significant desulfurization effect.
Supplementary carbon source is significant in selecting suitable carburant to be poured into a mould for the phosphorus pig iron, and carburant chooses whether
Rationally, carbon absorption rate and production cost will be directly influenced.The carburant of high-quality should possess granular size and be applicable, and real density is closed
Suitable, porosity is big, and infiltration rate is fast；Chemical composition is pure, and the high and low sulphur of fixed carbon content, trace element are atomic, and absorptivity is high；
Product degree of graphitization is high, the characteristic such as crystal structure of graphite is good.Solid carbon is from aluminium electroloysis waste cathode carbon block through vacuum metallurgy
Treatment is obtained, and waste cathode carbon block is that electrolytic cell stopping production overhaul after 1000~2000 days run is obtained.Because cathode carbon pieces are pressed
Percent by weight is mainly by about 50% electric calcined anthracite, 40% graphite it is broken and roasting it is broken, and 10% binding agent through kneading,
1200 DEG C of high-temperature roastings are formed, and the electric calcined anthracite for using is formed through 1800~2000 DEG C of calcinings, with graphite higher
Change degree, conducts electricity very well.To GS-3 in graphite cathode carbon block non-ferrous metal industry standard (YS/T 623-2012) used for aluminium electrolysis
The requirement of resistivity is no more than 35 μ Ω m, and the requirement to GS-5 resistivity is no more than 30 μ Ω m.Vacuum metallurgy method is
Refer to a kind of vacuum distillation smelting process carried out to material using metallurgical furnace under vacuum or inert gas shielding.Vacuum metallurgy sets
It is standby to be mainly made up of heater, crystallizer, vacuum plant, chilled water unit etc..With the useless negative electrode of vacuum metallurgy method process aluminum electrolytic
The fine separation of charcoal and electrolyte can be realized, the carbon content for obtaining is high, and energy consumption is low, pollution-free, and technological process is simple, feasible.
Solid carbon is mixed to be fitted on to melt down carry out in the phosphorus pig iron and increases charcoal desulfurization by the embodiment of the present invention as carburetting desulfurizing agent, is capable of achieving significantly to carry
Carbon element content high, reaches the purpose of carburetting, while the CaF in solid carbon2, NaF can play the effect of desulfurization again.
In addition, in order that melt down the phosphorus pig iron by carburetting adjusting component, determining the consumption and addition manner of carburant very
It is important, optimal carburant consumption is only determined, can be only achieved most economical preferable carburetting effect.Research shows, when carbon is worked as
When amount is close to 4.3, close to 1, molten iron flow now reaches optimal effect to eutectic degree, and the absorptivity of carbon is with carburant
Consumption is presented positively related relation within the specific limits, and after carburant reaches to a certain degree, absorptivity decline occurs and becomes on the contrary
Gesture, because unnecessary graphitic carbon can only be scaling loss or drain with slag.It was found that increasing can be calculated by equation below
The consumption of carbon agent：
G=G × (X2-X1)/(C×d)；
In formula：G-carburant addition, kg；G-weight of molten iron, kg；X1-foundry return phosphorus content, %；After X2-carburetting
Phosphorus content (carburetting desired value), %；C-carburant phosphorus content, %；The absorptivity of d-carbon, %.
Specifically, after being promoted to melting by original 2.0%~2.2% for the carbon content for making the phosphorus pig iron after melting down
3.0%~3.5% target, according to above formula, calculating the doping of additive in the embodiment of the present invention, to account for phosphorus pig iron raw material total
The 0.8%~2.0% of weight.
And, the size of carburant granularity also has an impact to the assimilation effect of carbon, and particle is smaller, easier in the phosphorus pig iron
Fully dissolved in melt, but in practical application, carburant is added in high temperature phosphorus molten pig iron, is added after either first adding still
Enter, carbon particle can be kicked up with high-temperature furnace gas, it is impossible in all dissolving in molten iron in a short time, can produce material Physical Loss or Damage and
Chemical scaling loss.Therefore, the mode that the embodiment of the present invention employs briquetting mixes carbon material with binding agent, melting promotor, compacting
Into pelletizing, used in intermediate frequency furnace.
The feed postition of carburant has material impact, the even obtained addition of the embodiment of the present invention to the casting yield of carbon
Agent, if simple additive to be added to intermediate frequency furnace bottom or top, cannot all realize quick, uniform melting in a short time,
In actual production, relatively low carbon casting yield is shown as.To avoid this problem, the embodiment of the present invention from proposing layering and add
Method, will ensure the bottom for additive during specific implementation, to melt down the phosphorus pig iron, middle each layer can be handed over according to actual conditions for the superiors
Element raw material and additive that for laying, other need to be supplemented.The paving mode of this layering had both avoided directly large batch of toward iron
Fed intake in water, anti-oxidation excessively carburetting DeGrain and the inadequate situation of casting carbon content occurs；It is simultaneously this uniform
Scattered feeding mode can reduce the airborne dust that additive is produced when in use again, it is to avoid cause workshop condition to pollute, realization green,
The purpose of efficient carburetting desulfurization.
On the other hand, the embodiment of the present invention add melting promotor effect be make additive in high-temperature fusant can rapidly " watt
Solution ", makes carbon be molten in high temperature liquid iron as early as possible.The melting promotor used in the embodiment of the present invention is carbonate, and its mechanism of action is：
Carbonate can discharge carbon dioxide in the melt, promote additive rapid melting and diffusion in melt.In addition, adding
Carbonate also has the purpose of desulfurization, below with to addition carbonate Na in molten iron2CO3As a example by, analyze its desulfurization principle：Wherein, it is main
Want chemical equation as follows：
Na2CO3→Na2O+CO2↑；
Na2O+FeS→Na2S+FeO；
Na2CO3+FeS→Na2S+FeO+CO2↑。
The Na of generation2S does not dissolve in iron liquid, floats up to bath surface and is removed；FeO is then reduced to Fe by C, and reaction equation is
FeO+C → Fe+CO ↑, reach desulfurization purpose.
Using fluorite (CaF2) purpose of desulfurization is diffusion, the mass transfer speed for improving reactant and product in slag phase
Degree.CaF2Slag can be consumingly diluted, viscosity coefficient of dross is reduced, strengthens mobility, the diffusion coefficient in phase be improved, in promotion slag phase
Reactant from fully being spread to interface inside slag phase, while making product CaS etc. quickly leave interface to being filled inside slag phase
Divide diffusion, accelerate the desulphurization reaction on interface to carry out to the right, reach the effect for making the phosphorus abundant desulfurization of pig iron liquid, reaction mechanism is such as
Under：
Fe+S→FeS；
CaF2+FeS→CaS+FeF2。
Feature of the invention and performance are described in further detail with reference to embodiments.
Embodiment 1
Embodiment 1 provides a kind of environment-friendly type phosphorus pig iron additive, and it uses following preparation process to obtain：
Prepare solid carbon：Waste cathode carbon block is processed through vacuum metallurgy, waste cathode carbon block particle diameter is 25mm, vacuum metallurgy bar
Part is：Vacuum is 10Pa, and metallurgical temperature is 1100 DEG C, and metallurgical time 2.5h obtains solid carbon, and wherein fixed carbon C content is
98.9%.The material phase analysis figure of the solid carbon is as shown in figure 1, as seen from Figure 1, the solid carbon is main by C, CaF2, NaF groups
Into.
Prepare raw material：9.65kg carbon materials (select granularity in the solid carbon of below 5mm, the solid carbon is by through vacuum
The solid carbon that Metallurgical processing is obtained is sieved, and is obtained by 5mm screen clothes), 0.3kg binding agents, the binding agent be according to
Sodium metasilicate：(starch+sodium carboxymethylcellulose)=1:1.5 ratio is configured, and 0.05% melting promotor (selects sodium carbonate).
Preparation process：Starch, sodium carboxymethylcellulose and 100 DEG C of water are pressed 7:1 mass ratio mixing, is quickly stirring
Lower addition sodium metasilicate is mixed, and adds sodium carbonate, stir 0.5h, naturally cool to room temperature, obtain binding material；Solid carbon is sprinkled into
In binding material, stirring 5min is prepared into additive paste；Additive paste is pressed into pelletizing on marble forming machine, is selected a diameter of
The ball mould processed of 5mm, ball-making pressure is controlled to 12MPa；The pelletizing of acquisition is placed in 110 DEG C of baking oven and dries 0.5h, obtained final product
Additive.
In addition, realizing that phosphorous pig iron carbon increasing sulfur method is using the additive in the present embodiment：
Account for phosphorus pig iron raw material gross weight according to additive 0.8% carries out dispensing, specifically weighs 0.08kg additives, 10kg
Phosphorus pig iron raw material (phosphorus pig iron raw material percentage include 0.55% supplement ferromanganese, 5.4% supplement the pig iron,
0.05% supplement ferrosilicon, 94% melts down the phosphorus pig iron), the additive that will be made to be layered addition in the way of be placed in intermediate frequency furnace,
One layer of additive specifically is added in intermediate frequency furnace bottom, the ferromanganese for melting down the phosphorus pig iron, additive and supplement is then sequentially added, returned
The pig iron of the stove phosphorus pig iron, additive and supplement, melts down the ferrosilicon of the phosphorus pig iron, additive and supplement, is eventually adding residue and melts down phosphorus
The pig iron.
Directly carry out melting down melting, smelting temperature is controlled at 1400 DEG C, is stirred continuously during melting, the phosphorus life to molten condition
Molten iron carries out 2 slag hittings treatment, treats that temperature is come out of the stove cast be down to 1350 DEG C by, pours into a mould the phosphorus after preceding sampling analysis carburetting desulfurization
5 kinds of constituent contents in the pig iron.
Embodiment medium phosphoric iron content requirement (desired value) of table 1
| The phosphorus pig iron | C | S | Si | Mn | P |
| Content requirement (%) | 2.5~3.6 | ＜ 0.2 | 2.0~3.0 | 0.3~0.9 | 0.8~1.6 |
The forward and backward phosphorus pig iron content detection result of carburetting desulfurization in the embodiment 1 of table 2
Direct-reading spectrometer testing result shows：The carbon content in the phosphorus pig iron after carburetting desulfurization have significant increase (from
3.3%) 2.0% rise to, and sulfur content decreases drastically (be reduced to 0.2% from 0.5%), has reached expected carburetting and has taken off
Sulphur target, meanwhile, there is not carbon particle in carburetting sweetening process and fly upward, and the limpid scum silica frost of molten iron is few, good fluidity.
Embodiment 2
Embodiment 2 provides a kind of environment-friendly type phosphorus pig iron additive, and it uses following preparation process to obtain：
Prepare solid carbon：Waste cathode carbon block is processed through vacuum metallurgy, waste cathode carbon block particle diameter is 20mm, vacuum metallurgy bar
Part is：Vacuum is 20Pa, and metallurgical temperature is 1000 DEG C, and metallurgical time 2h obtains solid carbon, and wherein fixed carbon C content is
98.1%.
Prepare raw material：9.8kg carbon materials (select granularity in the solid carbon of below 5mm, the solid carbon is by through vacuum smelting
The solid carbon that gold treatment is obtained is sieved, and obtained by 5mm screen clothes), 0.15kg binding agents, the binding agent is according to fluorine
Sodium metasilicate：(starch+polyvinyl alcohol)=1:2 ratio is configured, and 0.05kg melting promotors (select sodium carbonate).
Preparation process：Starch, sodium carboxymethylcellulose and 100 DEG C of water are pressed 8:1 mass ratio mixing, is quickly stirring
Lower addition sodium metasilicate is mixed, and adds melting promotor sodium carbonate, stir 1h, naturally cool to room temperature, obtain binding material；By solid carbon
It is sprinkled into binding material, stirring 10min is prepared into additive paste；Additive paste is pressed into pelletizing on marble forming machine, selection is straight
Footpath is the ball mould processed of 10mm, and ball-making pressure is controlled to 18MPa；The pelletizing of acquisition is placed in 180 DEG C of baking oven and dries 2h, i.e.,
Obtain additive.
In addition, realizing that phosphorous pig iron carbon increasing sulfur method is using the additive in the present embodiment：
Account for phosphorus pig iron gross weight according to additive 2.0% carries out dispensing, specifically weighs 0.2kg additives, the life of 10kg phosphorus
(phosphorus pig iron raw material percentage includes 0.90% ferromanganese, 8.4% pig iron, 0.10% ferrosilicon to iron material, and 90.6% melts down
The phosphorus pig iron), the phosphorus pig iron of the additive that will make and supplement to be layered addition in the way of be placed in intermediate frequency furnace, specifically in intermediate frequency
Furnace bottom layer adds one layer of additive, then sequentially adds the ferromanganese for melting down the phosphorus pig iron, additive and supplement, melts down the phosphorus pig iron, adds
Plus the pig iron of agent and supplement, the ferrosilicon of the phosphorus pig iron, additive and supplement is melted down, it is eventually adding and remaining melts down the phosphorus pig iron.
Directly carry out melting down melting, smelting temperature is controlled at 1500 DEG C, is stirred continuously during melting, the phosphorus life to molten condition
Molten iron carries out 3 slag hittings treatment, treats that temperature is come out of the stove cast be down to 1400 DEG C by, pours into a mould the phosphorus after preceding sampling analysis carburetting desulfurization
5 kinds of constituent contents in the pig iron.
The forward and backward phosphorus pig iron content detection result of carburetting desulfurization in the embodiment 2 of table 3
Direct-reading spectrometer testing result shows：Carbon content has significant increase (to be risen to from 2.2% in the phosphorus pig iron
3.5%), sulfur content decreases drastically (be reduced to 0.3% from 0.7%), has reached expected carburetting desulfurization target, together
When, there is not carbon particle in carburetting sweetening process and fly upward, and the limpid scum silica frost of molten iron is few, good fluidity.
Embodiment 3
Embodiment 3 provides a kind of environment-friendly type phosphorus pig iron additive, and it uses following preparation process to obtain：
Prepare solid carbon：Waste cathode carbon block is processed through vacuum metallurgy, waste cathode carbon block particle diameter is 50mm, vacuum metallurgy bar
Part is：Vacuum is 30Pa, and metallurgical temperature is 1150 DEG C, and metallurgical time 2.5h obtains solid carbon, and wherein fixed carbon C content is
98.5%.
Prepare raw material：9.7kg carbon materials (select granularity in the solid carbon of below 5mm, the solid carbon is by through vacuum smelting
The solid carbon that gold treatment is obtained is sieved, and is obtained by 5mm screen clothes), 0.25 binding agent, the binding agent is according to aluminosilicate
Sodium：(sodium carboxymethylcellulose+polyvinyl alcohol)=1:2 ratio is configured, and 0.05kg% melting promotors (select potassium carbonate).
Preparation process：Starch, sodium carboxymethylcellulose and 80 DEG C of water are pressed 10:1 mass ratio mixing, is quickly stirring
Lower addition sodium metasilicate is mixed, and adds potassium carbonate, stir 0.5h, naturally cool to room temperature, obtain binding material；Solid carbon is sprinkled into
In binding material, stirring 10min is prepared into additive paste；Additive paste is pressed into pelletizing on marble forming machine, is selected a diameter of
The ball mould processed of 8mm, ball-making pressure is controlled to 16MPa；The pelletizing of acquisition is placed in 160 DEG C of baking oven and dries 1h, obtained final product and add
Plus agent.
In addition, realizing that phosphorous pig iron carbon increasing sulfur method is using the additive in the present embodiment：
Account for phosphorus pig iron gross weight according to additive 1.0% carries out dispensing, specifically weighs 0.1kg additives, the life of 10kg phosphorus
(phosphorus pig iron raw material percentage when melting down melting includes 0.8% ferromanganese, 8.0% pig iron, 0.05% silicon to iron material
It is iron, balance of to melt down the phosphorus pig iron), the additive and the phosphorus pig iron that will be made to be layered addition in the way of be placed in intermediate frequency furnace, specifically
It is to add one layer of additive in intermediate frequency furnace bottom, then sequentially adds the ferromanganese for melting down the phosphorus pig iron, additive and supplement, melts down phosphorus
The pig iron of the pig iron, additive and supplement, melts down the ferrosilicon of the phosphorus pig iron, additive and supplement, is eventually adding residue and melts down the phosphorus pig iron.
Directly carry out melting down melting, smelting temperature is controlled at 1450 DEG C, and the molten iron to molten condition is stirred continuously during melting
2 slag hittings treatment is carried out, treats that temperature is come out of the stove cast be down to 1400 DEG C by, pour into a mould the phosphorus pig iron after preceding sampling analysis carburetting desulfurization
In 5 kinds of constituent contents.
The forward and backward phosphorus pig iron content detection result of carburetting desulfurization in the embodiment 3 of table 4
Direct-reading spectrometer testing result shows：Carbon content has significant increase (to be risen to from 1.9% in the phosphorus pig iron
3.2%), sulfur content decreases drastically (be reduced to 0.2% from 0.6%), has reached expected carburetting desulfurization target, together
When, there is not carbon particle in carburetting sweetening process and fly upward, and the limpid scum silica frost of molten iron is few, good fluidity.
Embodiment 4
Embodiment 4 provides a kind of environment-friendly type phosphorus pig iron additive, and it uses following preparation process to obtain：
Prepare solid carbon：Waste cathode carbon block is processed through vacuum metallurgy, waste cathode carbon block particle diameter is 30mm, vacuum metallurgy bar
Part is：Vacuum is 15Pa, and metallurgical temperature is 900 DEG C, and metallurgical time 1.5h obtains solid carbon, and wherein fixed carbon C content is
98.0%.
Prepare raw material：9.65kg carbon materials (select granularity in the solid carbon of below 5mm, the solid carbon is by through vacuum
The solid carbon of Metallurgical processing is sieved, and is obtained by 5mm screen clothes), 0.25kg binding agents, the binding agent is according to silicic acid
Sodium：(starch+sodium carboxymethylcellulose)=1:1.8 ratio is configured, and 0.1kg melting promotors (select sodium carbonate).
Preparation process：Starch, sodium carboxymethylcellulose and 100 DEG C of water are pressed 9:1 mass ratio mixing, is quickly stirring
Lower addition sodium metasilicate is mixed, and adds melting promotor sodium carbonate, stir 0.5h, naturally cool to room temperature, obtain binding material；To claim
Good solid carbon is sprinkled into binding material, and stirring 5min is prepared into additive paste；Additive paste is suppressed into balling-up on marble forming machine
Group, selects the ball mould processed of a diameter of 5mm, ball-making pressure to be controlled to 14MPa；The pelletizing of acquisition is placed in 130 DEG C of baking oven
0.5h is dried, additive is obtained final product.
In addition, realizing that phosphorous pig iron carbon increasing sulfur method is using the additive in the present embodiment：
Account for phosphorus pig iron gross weight according to additive 1.8% carries out dispensing, specifically weighs 0.18kg additives, the life of 10kg phosphorus
Iron material (phosphorus pig iron raw material percentage includes 0.7% ferromanganese, 5.5% pig iron, 0.08% ferrosilicon when melting down melting,
It is balance of to melt down the phosphorus pig iron), the additive that will be made to be layered addition in the way of be placed in intermediate frequency furnace, specifically at intermediate frequency furnace bottom
Layer adds one layer of additive, then sequentially adds the ferromanganese for melting down the phosphorus pig iron, additive and supplement, melts down the phosphorus pig iron, additive
With the pig iron of supplement, the ferrosilicon of the phosphorus pig iron, additive and supplement is melted down, be eventually adding residue and melt down the phosphorus pig iron.
Directly carry out melting down melting, smelting temperature is controlled at 1420 DEG C, is stirred continuously during melting, to the molten iron of molten condition
2 slag hittings treatment is carried out, treats that temperature is come out of the stove cast be down to 1360 DEG C by, pour into a mould the phosphorus pig iron after preceding sampling analysis carburetting desulfurization
In 5 kinds of constituent contents.
The forward and backward phosphorus pig iron content detection result of carburetting desulfurization in the embodiment 4 of table 5
Direct-reading spectrometer testing result shows：Carbon content has significant increase (to be risen to from 2.6% in the phosphorus pig iron
3.5%), sulfur content decreases drastically (be reduced to 0.2% from 0.5%), has reached expected carburetting desulfurization target, together
When, there is not carbon particle in carburetting sweetening process and fly upward, and the limpid scum silica frost of molten iron is few, good fluidity.
In sum, the preparation method process is simple of the environment-friendly type phosphorus pig iron additive of the embodiment of the present invention, obtained to add
Plus agent low cost, the carburetting desulfurized effect to the phosphorus pig iron is good；The phosphorous pig iron carbon increasing sulfur method of the embodiment of the present invention, using above-mentioned
Additive carries out carburetting desulfurization to the phosphorus pig iron, and carbon absorption rate is high, desulfurized effect is good, while being effectively reduced phosphorous pig iron carbon increasing desulfurization
During material dust collector, improve workshop condition.
Embodiments described above is a part of embodiment of the invention, rather than whole embodiments.Reality of the invention
The detailed description for applying example is not intended to limit the scope of claimed invention, but is merely representative of selected implementation of the invention
Example.Based on the embodiment in the present invention, what those of ordinary skill in the art were obtained under the premise of creative work is not made
Every other embodiment, belongs to the scope of protection of the invention.
Claims (10)
1. a kind of environment-friendly type phosphorus pig iron additive, it is characterised in that it is made up of following raw material, and percentage is described
Raw material includes 95.5%~98.5% carbon material, 1.0%~3.5% binding agent and 0.5%~1.0% carbonate,
Wherein, the carbon material is the solid carbon obtained through vacuum metallurgy treatment waste cathode carbon block, and the binding agent is by mass ratio
It is 1:1.5~2 inorganic binder and organic binder bond composition.
2. environment-friendly type phosphorus pig iron additive according to claim 1, it is characterised in that the particle diameter of the waste cathode carbon block is
10~50mm；The solid carbon is main by C, CaF2, NaF composition, wherein C content be not less than 98%.
3. environment-friendly type phosphorus pig iron additive according to claim 1, it is characterised in that the inorganic binder includes alkali gold
Category silicate, fluosilicate, alumino-silicate, phosphate, metal alkoxide, magnesium fluosilicate, ammonium chloride, ammonium phosphate, zinc oxide, hydrogen-oxygen
Change at least one in aluminium, aluminium borate.
4. environment-friendly type phosphorus pig iron additive according to claim 1, it is characterised in that the organic binder bond includes forming sediment
In powder, sodium carboxymethylcellulose, polyvinyl alcohol, sodium bentonite, sodium humate, polytetrafluoroethylene (PTFE), butadiene-styrene rubber at least one
Kind.
5. a kind of preparation method of environment-friendly type phosphorus pig iron additive, it is characterised in that it includes procedure below：
Percentage, prepares raw material, and the raw material includes 95.5%~98.5% carbon material, 1.0%~3.5%
Binding agent and 0.5%~1.0% carbonate, wherein, the carbon material be through vacuum metallurgy treatment waste cathode carbon block obtain
The solid carbon for arriving, the binding agent by being 1 in mass ratio:1.5~2 inorganic binder and organic binder bond composition；
The organic binder bond and 80~100 DEG C of water are pressed 7~10:1 mass ratio mixing, adds the nothing under agitation
Machine binding agent, and the carbonate is added, 0.5~1.0h is stirred, room temperature is naturally cooled to, obtain binding material；By the charcoal
Cellulosic material mixes 5~10min with the binding material, obtains additive paste；Additive paste is pressed on marble forming machine
Pelletizing, ball-making pressure norm controlling is 12~18MPa, obtains pelletizing, a diameter of 5~15mm of pelletizing；The pelletizing is placed in
0.5~3.0h is dried in 110~180 DEG C of baking oven.
6. the preparation method of environment-friendly type phosphorus pig iron additive according to claim 5, it is characterised in that the solid carbon is pressed
It is obtained according to following methods：The waste cathode carbon block is placed in vacuum metallurgy furnace, distillation is vacuumized and heat, vacuum is 10~
50Pa, heating vapo(u)rizing temperature is 850~1200 DEG C, and heating distillation time is 1~3h, is distilled after finishing in the vacuum metallurgy furnace
Collected in body of heater and obtain the solid carbon.
7. a kind of phosphorous pig iron carbon increasing sulfur method, it is characterised in that it includes procedure below：
By the environment-friendly type phosphorus pig iron additive and phosphorus pig iron raw material as any one of Claims 1-4 being layered addition
Mode is placed in intermediate frequency furnace, and carries out melting.
8. phosphorous pig iron carbon increasing sulfur method according to claim 7, it is characterised in that the additive gross weight accounts for described
The 0.8~2.0% of phosphorus pig iron raw material gross weight.
9. phosphorous pig iron carbon increasing sulfur method according to claim 7, it is characterised in that the phosphorus pig iron raw material includes melting down
The Adding Way of the phosphorus pig iron and element raw material, the additive and phosphorus pig iron raw material is：First one layer is laid at the intermediate frequency furnace bottom
The additive, then lays element raw material and the additive described in multilayer successively, finally lays and melted down described in one layer phosphorus life
Iron.
10. phosphorous pig iron carbon increasing sulfur method according to claim 7, it is characterised in that the smelting temperature is 1400~
1500 DEG C, it is stirred continuously in fusion process；Phosphorus molten pig iron to molten condition carries out 2~3 slag hittings treatment, and temperature is down to 1350
~1400 DEG C of cast of coming out of the stove.
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